Losses in Fuel Cells

Fuel Cell Thermodynamics

 Thermodynamics
Nobel laureate Richard Feynmann said,
“ In physics today, we have no knowledge of what energy is.”

Self-consisting “laws” from fundamental assumptions based on

human experience.
Q: How to “prove” Newton’s Law or Schrodinger Equation?

Internal energy (U)

No movement in macroscopic view,
but microscopic movement exist.
• Kinetic energy
– M
Molecular
l l movement &
vibration
• Chemical (potential) energy
– Bonding between atoms
 Laws of Thermodynamics
First law: conservation of energy
d(Energy)univ = d(Energy)system + d(Energy)surroundings = 0
d(Energy)system = -d(Energy)surroundings
dU = dQ – dW
(dW)mech= pdV
dU = dQ – pdV

Second law: Entropy of a system increases (dSuniv≥0)

Macroscopic: dS=dQrev/T
Microscopic: S = k log Ω
k: boltzmann’s constant
Ω: No. of possible microstates accessible to the system
 Entropy Example

a) A perfect crystal of 100 atoms: only 1 microstate

(configuration)
S = k log Ω = k log 1 = 0
b) A crystal of 97 atoms with 100 lattice space:
Ω=100C3=1.6 * 105
S = 1.66 * 10-22 J/K
 Thermodynamic Potentials
Rules describe energy transfer form one form to another
Let’s define four potentials U(S,V), H(S,p), G(T,p),F(T,V) for the
variables
i bl SS, V
V, T
T, p
Starting from dU = dQ – pdV = TdS – pdV ⇔ U = U(S, V ) or

(T, p) (S, p) (T, V)

Thermodynamics Potential
 Enthalpy of Reaction
Heat of reaction STP (standard temperature & pressure)
dH = TdS + Vdp is defined as thermodynamic quantity
at 298.15 K (so-called
( room
⇔ dH = TdS = dQ (heat of reaction) temperature) and 1 bar (or 1 atm). All
= dU + dW for p=const the thermodynamic potentials defined
at STP are tabulated as reference
reference,
often denoted with superscript 0. (e.g.
For general reactions (molar based) ΔH0)
aA + bB -> > mM + nN
Δhrxn = { mΔh(M) + nΔh(N) } - { aΔh(A) + bΔh(B) }
similar for entropy: Δsrxn = {mΔs(M)+nΔs(N)}-{aΔs(A)+bΔs(B)}

Temperature dependency
 Gibbs Free Energy
Lab environment (p=const, T=const)
Among four thermodynamic potentials,
Gibbs energy difference drives the
spontaneous chemical reaction

Reaction:

A⇔B
Extent of a reaction ξ: amount of
substahce
b t h th thatt reacts
t ffrom A tto B and
d
vice versa dξ=-dnA=dnB

ΔG=0
ΔG 0 reaction
ti iis iin E
Equilibrium
ilib i
ΔG<0 reaction is in Forward direction
ΔG>0
ΔG 0 reaction is in Backward direction

by Dr. R. Fasching at Stanford University

 Gibbs Free Energy
Gibbs Energy: potential under constant p & T
G = H – TS
⇔ dG = dH – TdS – SdT
⇔ Δg = Δ h – TΔs (can be found from tables.)

Electrical work
dG = dU – TdS – SdT + pdV + Vdp
dU = TdS – dW
dU = Tds – (pdV + dWelec)
⇔ dG = – SdT + Vdp – dWelec
⇔ dG = – dWelec l
⇔ Welec = -Δgrxn
This is valid for any T & p not-changing through reaction

Voltage of electric work

Welec= EQ = EnF
F: Faraday number, n: number of electrons involved in reaction
⇔ E = -Δg/nF
 Gibbs Free Energy
Dimensional
analysis
Standard Electrode Potential

Cell p
potentials of most
reaction are tabulated
from reaction energy.

Ecell = ΣEhalf-reactions
Standard Electrode Potential
 Standard Electrode Potential

Hydrogen
y g fuel cell

Direct methanol fuel cell

Standard Electrode Potential
 Maximum Possible
Fuel Cell Efficiency
Efficiency

90
Fuel Cell
80

70
cy limit / %

60 ΔG TΔS
ε= = 1−
ΔH ΔH
50
Efficienc

Tlow
40
ε = 1−
30
Thigh
E

20
Carnot Limit
10

0
0 200 400 600 800 1000

Temperature / Celsius
 Temperature Effect

dG = − SdT + Vdp
⎛ dG ⎞
⎜ ⎟ = − S for const p
⎝ dT ⎠ p
⎛ d (Δg ) ⎞
⎜ ⎟ = − Δs (Δg = − nFE )
⎝ dT ⎠ p
⎛ dE ⎞ Δs
⎜ ⎟ =
⎝ dT ⎠ p nF
Δs
ET = E + (T − T0 )
nF

As Δs
A Δ is
i almost
l t constant
t t vs. temperature,
t t Ed
decrease with
ith iincreasing
i
temperature
 Pressure Effect

dG = − SdT + Vdp
⎛ dG ⎞
⎜⎜ ⎟⎟ = V for const T
⎝ dp ⎠T
⎛ d (Δg ) ⎞
⎜ ⎟ = −Δv (Δg = −nFE ) Pressure also has minimal effect
⎝ dT ⎠T
on reversible
ibl voltage.
lt
⎛ dE ⎞ Δv
⎜⎜ ⎟⎟ =
⎝ dp ⎠T nF
⎛ dE ⎞ ΔnRT
⎜⎜ ⎟⎟ =
⎝ dp ⎠T nFp
Concentration Effect: Nernst Equation

by Dr. R. Fasching at Stanford University

Concentration Effect: Nernst Equation

by Dr. R. Fasching at Stanford University

 Nernst Equation
Consider the following electrochemical reaction

1A + bB ⇔ mM
M + nN
N
Using the definition of the chemical potential
pMm p Nn
Δg = (mμ M + mμ N ) − ( μ A + bμ B ) + RT ln 1 b
p A pB
pMm p Nn
Δg = Δg + RT ln 1 b
0

p A pB
(Δg = − nFE )
RT pMm p Nn
E=E − 0
ln 1 b : Nernst Equation
nF p A pB
In general, Nernst Equation can be expressed as:

RT ΠpProduct
vi
⎛ RT ΠaProduct
vi
⎞
E=E − 0
lln ⎜⎜ or E −
0
lln ⎟⎟
nF ΠpReactants
vi
⎝ nF Π aReactants ⎠
vi
 Nernst Equation: Examples
Consider the hydrogen-oxygen reaction at 120C
1
H 2 + O2 ⇔ H 2O( g )
2
Using the Nernst Equation E120C is calculated
RT p H 2O consideringg
E=E 120 C
− ln temperature effect
nF pH 2 pO1/22
Δs
ET = E + (T − T0 )
nF
F

Q: At STP, how to calculate the voltage? (when water is liquid)

1
H 2 + O2 ⇔ H 2O(l )
2
A: For pure component
component, activity = 1 (read the textbook)
textbook). Thus
RT 1
E=E − 0
ln
nF pH 2 pO1/22
 Concentration Cell

H 2 ( h. p.) ⇔ H 2( l . p.)

From Nernst Equation:

y
RT pH 2
E=E − 0
ln x
nF pH 2
−8
8.314 ⋅ 298.15 10
= 0− ln
2 ⋅ 96400 100
= 0.296V

Q H
Q: How a ffuell cellll without
ith t chemical
h i l reaction
ti iis possible?
ibl ?
What is the driving force?

A: Electrochemical potential will answer your question.

 Electrochemical Potential
In concentration cell, concentration gradient will
drive the migration (or diffusion) of hydrogen.
Previously, we found chemical potential is:

Thus, high pressure hydrogen has higher

chemical potential. The difference in chemical
potentials generates the voltages in the cell.

More conveniently, we may use “electrochemical potential” defined as

~
μi = μi + zi Fφi = μi + RT ln p + zi Fφi
0
 Electrochemical Potential
At electrochemical equilibrium, the net change in the electrochemical
potential is 0. (Remember Δg=0 at chemical equilibrium)
⎛ ⎞ ⎛ ⎞
⎜ ∑ν i μ~i ⎟ − ⎜ ∑ν i μ~i ⎟ =0
⎝ i ⎠ products ⎝ i ⎠ reactans
⎛ ⎞ ⎛ ⎞
⇔ ⎜ ∑ν i μi ⎟ − ⎜ ∑ν i μi ⎟ = − zi FΔφi
⎝ i ⎠ products ⎝ i ⎠ reactans

From this fact, you may re-derived the Nernst Equation as:

Δg 0 RT ΠpProduct
vi
Δφe − = E = − − ln
nF nF ΠpReactants
vi

RT Π p vi
= E0 − ln Product
nF ΠpReactants
vi
R t t
 Heat Dissipation by Fuel Cells
P = ΔH N& − P
Heat L

Pheat : Heat rejection rate by fuel cell

ΔH : Reaction enthalpy
N : Product generation rate
PL : Fuel cell load

1. Entropy loss

PTherm = T ΔS N&

2. Internal loss in fuel cells: activation, ohmic, concentration losses

3. Heat of condensation

Pcon = ΔH con N&

Heat Dissipation by Fuel Cells
Heat Dissipation by Fuel Cells
Heat Dissipation by Fuel Cells
 Maximum Possible
Real Fuel Efficiency
Cell Efficiency

EH
ε real = ε real × ε real × ε real
E
⎛ ΔG ⎞⎛ V ⎞⎛⎜ i / nF ⎞⎟
=⎜ ⎟⎜ ⎟⎜
⎝ ΔH ⎠⎝ E ⎠⎝ v fuel ⎟⎠
⎛ E ⎞⎛ V ⎞⎛ 1 ⎞ V
= ⎜⎜ ⎟⎟⎜ ⎟⎜ ⎟
⎝ E H ⎠⎝ E ⎠⎝ λ ⎠
λ = stoichiome
t i hi t i number
tric b
supplied fuel rate
=
consumed fuel rate
i λi
 Fuel Cells Stacks

Vtotal = Vcell × number of cells

I total = I cell
Ptotal = I total × Ptotal = I cellVcell × number of cells
= Pcell × number
b off cells
ll